title: Is uracil aromatic? The enthalpies of hydrogenation in the gaseous and crystalline phases, and in aqueous solution, as tools to obtain an answer.
abstract: The enthalpy of hydrogenation of uracil was derived from the experimental enthalpies of formation, in the gaseous phase, of uracil and 5,6-dihydrouracil, in order to analyze its aromaticity. The enthalpy of formation of 5,6-dihydrouracil was obtained from combustion calorimetry, Knudsen effusion technique and Calvet microcalorimetry results. High-level computational methods were tested for the enthalpy of hydrogenation of uracil, but only with G3 was possible to obtain results in agreement with the experimental ones. It was found that uracil possesses 30.0% of aromatic character in the gaseous phase. Using both implicit, explicit, and hybrid solvation methods, it was possible to obtain a reference value for the enthalpy of hydrogenation of uracil in the aqueous solution and the effect of polarity and hydrogen bonds on the aromaticity of uracil was analyzed. The value of the hydrogenation enthalpy of uracil in aqueous solution was compared with the experimental value in the crystal phase, also dominated by polarity and hydrogen bonds, derived from combustion calorimetry results. The supramolecular effects on the crystal lattice were explored by the computational simulation of π-π staking dimers and hydrogen bonded dimers.
authors.affiliation: Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto , Rua do Campo Alegre, 687, P-4169-007, Portugal.
authors.forename: Tiago L P
authors.initials: TL
authors.lastname: Galvão
authors.forename: Inês M
authors.initials: IM
authors.lastname: Rocha
authors.forename: Maria D M C Ribeiro
authors.initials: MD
authors.lastname: da Silva
authors.forename: Manuel A V Ribeiro
authors.initials: MA
authors.lastname: da Silva
mesh_terms: D003460:Crystallization; D005740:Gases / Q000737:chemistry; D006860:Hydrogen Bonding; D006865:Hydrogenation; D015394:Molecular Structure; D011789:Quantum Theory; D012996:Solutions; D013816:Thermodynamics; D014498:Uracil / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D005740:Gases; D012996:Solutions; D014867:Water; D014498:Uracil